Method for the production of a supported chromium-cobalt-palladium oxide exhaust catalyst



United States Patent U.S. Cl. 252-455 4 Claims ABSTRACT OF THE DISCLOSURE A method of producing an exhaust gas catalyst comprises the consecutive impregnation of a support with chromium and with cobalt-palladium salt solutions, said impregnations being separated by a drying step and followed by calcination.

This application is a division of my earlier filed application Ser. No. 255,658, now abandoned.

This invention relates to an auto exhaust catalytic system. In one particular aspect, it relates to a catalyst having improved hydrocarbon conversion activity and increased thermal stability.

The air pollution problem is not new. However, in recent years the problem has become aggravated. The air in most cities contains substantial amounts of oxides of nitrogen and products of the incomplete combustion of organic fuels. In the presence of sunlight, photolysis of the oxides of nitrogen leads to the formation of measurable quantities of ozone. The ozone, in turn, reacts with various organic pollutants to form compounds which can cause the many undesirable manifestations of smog, such as eye irritation, visibility reduction and plant damage.

When meteorological conditions prevent the rapid dispersion of organic pollutants, a smog condition results. Furthermore, it is now known that in many cities, a major portion of organic pollutants are derived from unburned or partially burned gasoline in auto exhaust.

Carbon monoxide is another pollutant of much concern because of its toxic nature. It also is derived mainly from exhaust emissions.

Numerous attempts have been made since the advent of the automobile to render harmless and unobjectionable the exhausts from internal combustion engines. Various filters, mufilers, etc. have been designed in an effort to solve this problem. To date, none have met with success complete enough for practical application. One of the main problems is that systems which appear to work initially very quickly become contaminated and consequently useless. It is not feasible to install catalytic systems which must be periodically removed and rejuvenated because of the cost involved.

It has been realized that the only practical way to treat exhaust fumes to reduce air pollution is to oxidize hydrocarbons to carbon dioxide and water and to oxidize carbon monoxide to carbon dioxide.

A wide selection of oxidation catalysts has been produced in the past varying both in chemical composition and physical structure. With respect to chemical composition, the ability of a wide variety of metals and metal oxides, either alone or in combination, to catalyze the complete oxidation of hydrocarbons has been noted.

To be adequately efficient in the removal of hydrocarbons and carbon monoxides from auto exhaust gases and to meet the standards of maximum emission currently under consideration in the legislatures of the various states, the catalyst for treating exhaust gases must become eflicient within a very few minutes after engine start-up and must maintain its activity throughout the various modes of engine Operation. A catalytic converter must maintain its catalytic activity for a period of not less than one year and preferably for two years or 20,000 miles of engine operation. The problem of excessively high temperatures which are obtained when high concentrations of pollutants are being oxidized must also be solved in this system. It is not unusual for catalyst temperatures to reach 1600 F. or higher. A normal catalytic system cannot withstand prolonged exposure to these temperatures without degradation of the catalyst.

The catalytic systems which have been devised to give satisfactory results for carbon monoxide conversion frequently suffer from relatively poor conversion of hydrocarbons. Since the ideal catalytic system gives a good conversion of both of these exhaust gas components, this problem is of prime importance.

We have found that an auto exhaust catalyst with good hydrocarbon conversion and carbon monoxide conversion activity can be prepared by combining chromia with a cobalt oxide-palladium oxidation catalyst.

The addition of palladium to the cobalt oxide type catalyst has a promotional effect. It is added to improve the cold start activity of the catalyst. The chromia is found to greatly improve the hydrocarbon activity of the catalyst. The addition of 1 to 20% chromia (Cr O definitely has a beneficial effect.

Broadly speaking, our process consists of selecting a suitable support, preferably in the form of nodules with a high surface area. The preferred size of these nodules is about 5 to 8 mesh or 8 to 10 mesh (the Tyler Standard Screen Scale). However, satisfactory results are obtained when the nodules have diameters of 3 to 10 mesh. After the support has been selected, it is impregnated with a soluble chromia source. The chromia impregnation is carried out so that the final catalyst will contain about 1 to 20 weight percent Cr O Suitable chromia salts for this impregnation include ammonium chromate, (NH CrO chromic acid, H CrO chromic acetate, Cr (C H O -H O, etc. The chromia-treated base is dried for a short period of time at about 260 F.

A second impregnation is then carried out with a cobalt salt-palladium salt solution. This solution is made up to prepare a final catalyst containing 4 to 16 weight percent cobalt oxide and 0.01 to 0.1 weight percent palladium. After the second impregnation, the drying step is repeated and the catalyst particles are then heated to about 1400 F. for from 3 to 19 hours in an atmosphere of air, steam, or a mixture of the two.

The :basic step in the preparation of the catalyst is the selection of a suitable base. The base or support for the catalyst should have a high surface area and be relatively porous material in order that maximum activity will be exhibited by the catalytic components. The support should also have good strength properties to avoid the problem of excessive attrition. Examples of suitable supports include alumina, silica-alumina, silica-magnesia, zirconia, zirconia-alumina, zirconia-magnesia, etc.

Particularly good results are obtained in using a gamma-type alumina as the catalyst support. This support may be used in a powdered, granulated, pilled or extruded form. A particularly desirable support is the gamma type alumina which is commercially available in the form of nodules. These nodules have a very desirable combination of properties. The crushing strength is quite high. They are porous and have a high surface area.

The size of the nodules also has some bearing on the activity of the catalyst. The preferred size of these nodules 3 is about 5 to 8 mesh (The Tyler Standard Screen Scale).

After the base has been selected, it is impregnated with a suflicient quantity of a chromium salt solution to deposit 1 to 20 weight percent and preferably 4 to 10 weight percent chromia on the catalyst. The chromia substantially improves the hydrocarbon activity of both the fresh catalyst (calcined 3 hours at 1400 F.) and the thermally aged catalyst (calcined an additional 16 hours at 1400 F.). The chormia is particularly beneficial when alumina is used as the catalyst support. The chormia coats the alumina and minimizes the formation of essentially inactive cobaltous and cobaltic aluminate. It also tends to keep the cobalt in its more active form, i.e., the cobaltic state. To reduce the reaction of cobalt with the alumina base most effectively, the chromia is added prior to the cobalt-palladium impregnation. However, it is also effective for this purpose if it is added at some other stage in the preparation. After the chromia impregnation, the wet nodules are dried at 260 F. in air.

After the nodules are dried, they are impregnated with a cobalt salt-palladium salt solution. The cobalt and palladium salts are present in amounts suflicient to furnish a final catalyst with 4 to 16 Weight percent cobalt oxide and 0.01 to 0.1 weight percent palladium. Any of the known soluble cobalt salts can be used in the preparation of the catalyst. Suitable examples include the acetate, bromide, chloride, cyanide, sulfate, thiocyanate, etc. Because of its availability and comparatively low cost, the preferred salt is the nitrate. Suitable palladium salts for this preparation include palladium bromide, palladium chloride, palladium fluoride, palladium nitrate, palladium sulfate, etc.

After the cobalt salt-palladium salt impregnation, the nodules are again dried at 260 F. in air, steam or a mixture of air and steam.

The final step in the process is calcination. Generally, 3 to 19 hours at about 1400 F. is sufficient.

The catalyst prepared according to this invention exhibits good thermal stability and excellent hydrocarbon activity.

The catalysts were evaluated by determining the per cent conversion of a mixture containing 3.85% carbon monoxide, 1000 parts per million of normal hexane, 4.5% oxygen, 10% water and the balance nitrogen.

The gases were passed through the catalyst at a gaseous hourly space velocity of 5000 volumes of gas per volume of catalyst per hour.

The activity index of the catalyst for either carbon monoxide or hydrocarbon conversion is determined by measuring the area under an activity curve in the range of the average catalyst temperature, 350850 F., and calculating what percentage this area constitutes of the area under the ideal activity curve. Ideal activity is defined as 100% conversion throughout this temperature range. Thus, the activity index may vary from 0, which indicates no activity, to 100 which would indicate socalled idea activity.

Our invention will be further explained by the following specific but non-limiting examples.

Example I A generally useful method of preparing the catalyst of our invention is illustrated in this example.

The chromia impregnating solution was prepared by dissolving 83.0 grams of ammonium chromate in 350 cc. of deionized water. This solution was then used to impregnate 885 grams of commercially available alumina monohydrate nodules. The wet nodules were dried at 260 F.

The cobalt-palladium impregnating mixture was prepared by mixing 3.0 cc. of a 10% Pd(NO solution with 388.0 grams of Co(NO -6H O. The impregnation was carried out by mixing the material with the hot nodules just as they came out of the drying oven at 260 F. and allowing the salts to melt onto the support.

4 The nodules were again dried at 260 F. and then calcined for 3 hours at 1400 F.

The final catalyst contained 5 weight percent Cr O 10 weight percent C00 and 0.03 weight percent Pd.

Example H In this run a catalyst containing 7.5% chromia was prepared.

A quantity of 860 grams of alumina monohydrate nodules was impregnated with a solution containing 124.0 grams of (NH Cr O in 350 cc. of deionized water. The Wet nodules were dried at 260 F.

The hot nodules were reimpregnated just as they came from the oven by allowing a mixture of 388.0 grams of Co(NO -6H O and 3.0 cc. of a 10% Pd(NO solution to melt onto the hot support. The nodules were again dried at 260 F. and then calcined for 3 hours at 1400 F.

The composition of the final catalyst was 7.5 weight percent Cr O 10.0 weight percent C00 and 0.03 weight percent Pd.

ExampleIII A catalyst was prepared in this run to contain 10.0% Cr O A total of 834 grams of alumina monohydrate nodules was impregnated with 166.0 grams of (NH4)2CT207 The wet nodules were dried at 260 F.

The hot nodules were then impregnated with a mixture containing 388.0 grams of Co(NO -6H O and 3.0 cc. of a 10% Fd(N )2 solution. The mixture was allowed to melt onto the hot support. The nodules were then redried at 260 F. and finally calcined for 3 hours at 1400" F.

The composition of the final product was 10.0 weight percent Cr O 10 weight percent C00 and 0.03 weight percent Pd.

Example IV In this run, a slightly modified technique was used to prepare the catalyst.

250 grams of alumina monohydrate nodules were impregnated with 49.6 grams of (NHQ Cr O and enough deionized water to bring the mass to incipient wetness. The nodules were then dried at 260 F.

The hot base was reimpregnated with a melted solution of 117 grams of Co(NO '6H O and 0.9 ml. of 10% Pd(NO solution. The impregnated nodules were dried at 260 F. and calcined for 3 hours at 1400 F.

The product contained 10 weight percent Cr O 10 weight percent C00 and 0.03 weight percent Pd.

Example V In this series of runs, a one step impregnation technique was used to prepare catalysts with zirconia as a support. A total of 89 grams of zirconia pills was impregnated with a solution containing 38.9 grams of Co(NO -6H O, gBOcc. of a 10% Pd(NO solution and 1.33 grams of The mass was dried at 260 F. and calcined for 3 hours at 1400 F.

The final composition of the catalyst was 10.0 weight percent C00, 0.03 weight percent Pd and 1.0 Weight percent Cr O A second catalyst was prepared using the same technique and conditions.

A solution containing 38.9 grams of Co(NO -6H O, 0.3 cc. of a 10% Pd(NO solution and 3.95 grams of CrO was used to impregnate 87 grams of zirconia pills.

The impregnated base was dried at 260 F. and then calcined for 3 hours at 1400 F.

The product contained 10 weight percent C00, 0.03 weight percent Pd and 3.0 weight percent Cr O These two catalysts, containing 1 and 3 weight percent Cr O were combined in such proportions that the active ingredients were present in amounts equal to 10.0 weight percent C00, 0.03 weight percent Pd and 2.0 weight percent C130 Example VI A catalyst containing no chromia was prepared accord- A total of 660 ccs. of catalyst was placed in the muffler which had a diameter of 3 inches. The mufiier was inserted in the exhaust line in such a manner that it acted as a downflow reactor. Thermocouple were placed at various points through the catalyst beds of the muflier. The

ing to the technique decribed in Example I. This catalyst 5 was compared with those containing chromia in order to amount of carbfm e bemg Passed through i demonstrate the superior performance of the catalysts of mPffler was vfmed by adlustmg the carburetor to our invention tam the maximum catalyst temperature between 1400 An 885 gram quantity of alumina monohydrate nodules and l450 F. Excess air was added to insure complete comwas heated to 260 F. The nodules were then impregnated q that aboqt to stanqard cublc feet Per with a mixture containing 3880 grams of (300109261120 minute. Usually, the time for this test 13 about 93 to 100 and 3() of a 10% Pd(NO3)2 solution by allowing the hours. However, it will be seen from the data below that mix to melt onto the hot Support the catalyst with no chromia failed at 25 hours. The

The material was then dried at 260 F. and finally calchrfmua catalyst was tested for the 93 to 100 hour cined for 3 hours at 1400 F. 15 Penod- The final catalyst contained 109 Weight percent C00, The evaluations of the catalysts were made on the basis and 0'03 Weight percent of activity of the catalysts for hydrocarbon and carbon monoxide conversion before and after the time in the Example VII muffier of the single cylinder engine. The comparative The performance of the catalyst of our invention was data Was collected using the catalyst of this invention P evaluated by measuring the hydrocarbon and carbon pared to contain Weight Pcrcent z a, Weight monoxide conversions of the individual catalysts and by Pement C00 and Weight Percent Pd on alumina determining the activity indices *by the tests described nodules (designated Catalyst and a cobalt OXidepreviously. palladium catalyst containing no chromia (designated The results of these tests are set out below: Catalyst B). This catalyst contained 13.0 weight percent TABLE I Example I II III IV v VI Wt. percent CI203 5.0 7. 5 10. 0 10.0 3. 0 0. 0 Wt. percent C00.-- 10. 0 10.0 10. 0 10.0 10. 0 10.0 Wt. percent Pd 0.03 0. 03 0.03 0. 03 0. 03 0.03 Percent conversion of hydrocarbons at 750 F 92 95 98 99 96 67 Activity index:

Carbon monoxide.. 73. 2 71. 6 64. 2 74. 9 74. 2 73. 7

Hydrocarbons 50. 4 48. 6 51. 5 66. 0 47. 9 33. 2

These data clearly show the improved performance in C00 and 0.04 weight percent Pd on alumina nodules. The hydrocarbon conversion shown by the catalyst of this indata is set out in Table II below: vention. The conversion is about greater at 750 F. TABLE II than the catalyst without chromia.

The effect of the greater hydrocarbon conversion is v ty d ces particularly obvious from the hydrocarbon activity index. After 93 to 100 The carbon monoxide activity index is roughly the same Fresh hours in the mufiier for the catalysts with and without chromia. Hydrom Example VIII Catalyst 00 carbons C0 carbons The superior performance of the catalyst of our inven- 5M Fust i311 tion was shown by comparing the catalyst prepared in 32 4 Fistbed- Example I with an auto exhaust catalyst which contained 13 weight percent 000 and 0.04 weight percent Pd on 'g si zg i igf 611d M25 h s catalyst was completely alumina nodules.

In this series of runs, the catalysts were evaluated in a T e advantages of the chromia in our catalyst are mufiier system in which the exhaust gases passed from the Shown y a COIHPaIiSOH 0f the data 011 the activity of top to the bottom of th system Th catalysts r b. Catalysts A and B. Catalyst A retains its activity when iected to actual operating conditions by placing the cataexposed to operating conditions as long as 93 to 100 lysts on screens in the two beds of the mufiler where one hours. Catalyst B, on the other hand, loses activity comcatalyst is above the other. The exhaust stream of a single pletely after 25 hours. cylinder engine and auxiliary air were passed through the The data also show that the catalyst of our invention catalyst beds. has good resistance to effects of lead in the exhaust The engine was operated on a commercial premium gases. The activity remains good even after long exposure gasoline containing 3.0 ml. of tetraethyl lead per gallon. to lead.

The engine used in the test was a Palmer PW-27 water We claim:

cooled single cylinder engine with a bore of 3.25 inches and a displacement of 27 cubic inches. The engine was automatically controlled to operate on a repetitive two minute cycle consisting of approximately 30 seconds at 1. A method for preparing a catalyst suitable for use in a catalytic system for oxidation of air pollutants in auto exhaust gases which comprises adding a sufiicient quantity of a chromium salt solution to give a final catalyst conidle (500 r.p.m.) and 90 seconds at cruise (1800 r.p.m.). taining to 20 weight percent chromia to a support selected from the group consisting of alumina, silica-alumina, silica-alumina-magnesia, and zirconia, drying the wet support, reimpregnating the material with a solution containing sufiicient cobalt salt to provide a final catalyst containing 4 to 16 weight percent cobalt oxide and sufiicient palladium salt to provide a final catalyst containing 0.01 to 0.1 weight percent Pd, drying the Wet support, calcining the dried catalyst at about 1400 F. for about 3 to 19 hours and recovering the catalyst for use in the system.

2. A process according to claim 1 wherein the cobalt salt is selected from the group consisting of the acetate, bromide, chloride, cyanide, nitrate, sulfate and thiocyamate.

3. A process according to claim 1 wherein the chromium salt is selected from the group consisting of ammonium chromate, chromic acid ammonium dichromate and chromic acetate.

4. A process according to claim 1 wherein the palladium salt is selected from the group consisting of palladium bromide, palladium chloride, palladium fluoride, palladium nitrate and palladium sulfate.

References Cited UNITED STATES PATENTS 3,133,029 5/1964 Hoekstra 252-466 10 DANIEL E. WYMAN, Primary Examiner PHILIP M. FRENCH, Assistant Examiner US. Cl. X.R. 

